Organic heterocyclic quaternary ammonium compounds



Fatented Feb. 20, 1 951 RGAN1QHE'EER CLIC Q E N R ,AMMoNrUM cor/IPoUNns ,rAdrie11;S.-l1u Bois, Jersey City, N. .L, and Emery I. Valko, New Eorlr, N. Y., assignors to Onyx Oil & Qhemical C ompany, .lersey City, N .,J., a

corporation .of Delaware No Drawing. Application December 28, 1946, Serial No. 719,140

6 Claims.

Our invention relates to-novel organic :compounds useful as cationic surface active agents or germicides and .as intermediates in the preparation of other compounds possessed of even greater surface active and germicidal properties.

This application is in part a continuation of our application, Serial No. 564,548, filed November 21, 1944, now abandoned.

Our compounds are characterized in that they contain a nitrogen atom linked to the terminal carbon atom in the (CH2)1L portion of the group in which R is an alkyl group containing at least five carbon atoms and n is an integer greater than 1.

The compounds .of our invention conform to the formula ECO- 7 2 4cm) i) in which R and n have the same-significanceas above, X represents a halogen atom, most suitably bromine or chlorine, and in which the circle indicates that the nitrogen atom is part of a heterocyclic ring system which may involve one or two rings.

As exemplary of such compounds may be mentioned: hexoyl phenethyl pyridinium bro.- mide, lauroyl phenethyl pyridinium bromide,

-cc tanoyl phenethyl pyridinium bromide, lauroyl phenylpropyl quinolinium bromide, undecoyl phenylbutyl quinolinium chloride, hexadecoyl phenylpropyl picolinium bromide, octadecoyl phenethyl isoquinolinium bromide, the chlorides and bromides of N-hexoylphenethyl morpholine, heptoyl phenethyl pyridinium bromide, etc.

The compounds are best, but not necessarily, prepared by reacting the corresponding alkoylphenylalkyl halides Boo-Gama):

accordance with the application ;cf-whi ch -,the instant application is a continuation, by the acylation of the corresponding halogenated? alkyl phenyl compounds, i. ,e. halogenated, aikyl phenyl compounds in which the halo alkyl radical contains at least two carbon atoms and in which the halogen atom is attached tothe terminal carbon atom of the halo-alkyl group. Depending upon the product ultimately desired, the compound acylated may or may not contain one or more nuclear substituents in addition ,to the halogenated alkyl radical. The acylation reaction may be effected 'using :a Friedel-Crafts type catalyst, e. g. aluminum chicride, boron fluoride, etc., and at a relatively low temperature. The precise temperature em:- ployed depends upon the particular reactants, but is usually within the range 10 C. to 60 C. Inert solvents conventionally used in conjunction with Friedel-Crafts type catalyst, carbon disulfide, for instance, may be utilized to maintain the reaction mixture at the desired temperature.

The reaction between the alkoyl phenylalkyl halide and the amine proceeds; at a temperature determined chiefly by the reactivity ofthe-nitrogen-containing reactant and the length of the reaction period is similarly determined. Usually a temperaturewithin the range C.-140 ,C. and a reaction period of from 30 minutes to .several hours are required, but in some cases the reaction may go to completion within a short time even at room temperature. It is our practice to use either an equimolecular quantity or an excess .of the nitrogen-containing reactant. Solvents such as mono and po-lyhydroxy alcohols may be employed wheretheuse of a solvent is indicated or is feltto be desirable. As between the alkoyl phenylalkyl chlorides and'the alko-yl phenylalkyl" bromides, we prefer the latter as they seem to be somewhat more reactive.

Our invention is illustrated by the following specific examples which are not to be taken as in any way limitative of the scope thereof:

Example I 539 parts by weight of lauroylphenethyl bromide are heated with parts by Weight of pyridine at 120 C. for 2 hours. The resulting quaternary ammonium compound, lauroyl phenethyl pyridinium bromide, is soluble in water and its aqueous solution foams copiously. When tested for its antibacterial properties in accordance with the method described in Circular No. 198 of the United States Department of Agriculture, a (Ii-.-

3 lution of 110,000 kills Eberthella typhosa' and a dilution of 1:20,000 kills Staphylococcus aureus at in 10 minutes.

Example II 162 parts by weight of caprylyl phenethyl bromide and parts by Weight of pyridine are reacted at 40 for 6 hours to obtain caprylyl phenethyl pyridinium bromide. This Water soluble product shows a killing dilution of 1:1700 against Eberthella typhosa.

Example III 290 parts by weight of caproyl phenethyl bromide and parts by weight of pyridine are reacted at C. for 5 hours to obtain caproyl phenethyl pyridinium bromide. The product kills Eberthella typhosa in a dilution of 1:1,000.

Example IV Example V 1 parts by weight of caproyl phenylethyl bromide and 79 parts by weight of pyridine are heated at 140 C. for 6 hours. The product is washed with ether in order to remove the impurities consisting mostly in unreacted reagents. The remaining material consisting predominately .of caproyl phenethyl pyridinium bromide is soluble in water. When tested for its anti-bacterial property according to the method described in Circular No. 198 of the United States Department of Agriculture it kills Eberthella typhosa in 1: 1,900 dilution at 20 C. in 10 minutes.

We claim:

1. Organic chemical compounds conforming to the formula RCOO(CH2),.A

in which R represents an alkyl group containing at least 5 carbon atoms, n is an integer greater than 1, and A is a quaternary ammonium radical of the group consisting of the pyridinium, quinclinium, isoquinolinium, morpholinium and picolinium radicals, the nitrogen atom of the quaterthe terminal carbon atom of the (CHzM group, and also to a halogen atom.

2. Method of preparing organic chemical compounds conjorming to the formula coo-OmmM-a in which R represents an alkyl group containing at least 5 carbon atoms, 12 is an integer greater than 1, and A is a quaternary ammonium radical of the group consisting of the pyridinium, quinclinium, isoquinolinium, morpholinium, and picolinium radicals, the nitrogen atom of the quaternary ammonium radical being linked directly to the terminal carbon atom of the (CH2)n portion of the group and also to a. halogen atom, the method comprising reacting a heterocyclic nitrogen compound of the class consisting of pyridine, quinoline, isoquinoline, morpholine and picoline with a compound conforming to the formula RC 00- 1112) nX in which R and n have the same significance as in the'preceding formula and X represents a halogen atom.

3. Lauroyl phenethyl pyridinium bromide ou 1 CHCH Br 4. Lauroyl phenethyl quinolinium bromide- CBS-CH (EH-OE 5. Caprylyl phenethyl pyridinium bromide. 6. Caproyl phenethyl pyridim'um bromide.

ADRIEN S. DU BOIS. EMERY I. VALKO.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS nary ammonium radical being linked directly to OTHER REFERENCES 

1. ORGANIC CHEMICAL COMPOUNDS CONFORMING TO THE FORMULA 